Gas sensor with tin monoxide disks

ABSTRACT

Gas sensor. The sensor is a single crystalline SnO disk and circuitry for measuring electrical resistance of the disk is provided. A change in resistance in the disk indicates adsorption of a gas on the disk&#39;s surface. The sensor is particularly adapted for detecting NO2 with high sensitivity and selectivity.

PRIORITY INFORMATION

This application claims priority to U.S. provisional application Ser. No. 61/825,603 filed on May 21, 2013, the contents of which are incorporated herein by reference in their entirety.

BACKGROUND OF THE INVENTION

This invention relates to gas sensors and more particularly to a gas sensor in which single crystal SnO micro-disks form the sensing element.

The increase in harmful gas emissions and the resultant threat to public health, particularly in urban environments, has stimulated research aimed at the development of highly sensitive and selective gas sensors suitable for air-quality monitoring [1]. NO_(x), CO, H₂S are considered particularly harmful to public health, even at low concentrations, given their negative impact on the human respiratory system [2,3]. Detection of these pollutant gases at ppm and ppb levels, with high sensitivity and selectivity, remains a major challenge [4]. While there are a number of means for detecting gases based on optical, gravimetric and electrical approaches, those based on monitoring changes in resistance of semiconducting oxides upon surface adsorption/desorption of gases (chemoresistance) offer key advantages including low cost processing, simple design and measurement, coupled with relatively high sensitivity [5,6,7,8,9].

SnO₂ has been the most highly investigated material in this class of sensors [10]. This research has included investigation of different fabrication approaches to form thin films[11], nano [12,13,14], mesoporous [15], and macroporous structures[16,17], as well as the impact of various catalysts and dopants on sensor response [18,19,20]. To achieve higher sensitivity and selectivity, more complex multilayered and metal functionalized structures based on SnO₂ have been reported [21,22,23]. Despite these efforts, it has been difficult to obtain simple devices which combine high sensitivity and selectivity with long-term stability.

SUMMARY OF THE INVENTION

The present invention is a gas sensor including a single crystalline SnO disk and circuitry for measuring electrical resistance of the disk, whereby change in resistance indicates adsorption of a gas on the disk's surface. It is preferred that the disks have a diameter in the range of approximately 100 nm to 100 μm. It is also preferred that the SnO disks have a [001] plane exposed to the gas. The sensor of the invention is particularly sensitive to detecting the presence of NO₂.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1a is a Field Emission gun scanning electron microscope (FEG-SCM) image of disks present in collected material after a sedimentation process.

FIG. 1b are high magnification images of isolated disks showing octagon-like disks.

FIG. 1c is a high magnification image of isolated disks having a rounded shape.

FIG. 2a is a Transmission electron microscopy (TEM) image of a typical faceted disk.

FIG. 2b is a High resolution transmission electron microscopy (HRTEM) image of the white square area in FIG. 2a . The inset is the SAD pattern of the faceted disk.

FIG. 3 is a graph of sensor signal versus time of the disk-like structures during cyclic exposure to 20-minute NO₂ pulses with increasing concentrations at 200° C.

FIG. 4 is a graph of sensor signal against operating temperature for the SnO disk-like structures at 100 PPM NO₂ in dry air. The inset shows the sensor signal at 100 PPM of NO₂, H₂, CO, and CH₄ at 200° C.

FIG. 5 constitutes graphs of intensity versus energy for X-ray Absorption Near Edge Structure (XANES) spectra for the SnO disks during sensor test simulation at 200° C. Curve a shows measurements performed in N₂ after three hours of stabilization. Curve b shows dry air inserted into the chamber followed by N₂ again. Curve d shows a standard SnO₂ spectrum for comparison.

FIG. 6 is a schematic illustration of a gas sensor using a SnO disk as the sensor element.

DESCRIPTION OF THE PREFERRED EMBODIMENT

While SnO₂ is one of most studied materials for gas sensors applications, to the best of the inventors' knowledge, no sensor response has been reported for tin monoxide, SnO. This lack of research is not surprising given the difficulty in synthesizing this phase and its thermal decomposition at temperatures above 400° C. [24,25]. SnO is reportedly a p-type semiconductor with a tetragonal litharge (alpha lead monoxide) structure, layered in [001] direction and a band gap between 2.5 and 3.0 eV [26,27]. We have synthesized SnO structures by a carbothermal reduction method, displaying both thermal and chemical stability for temperatures below 400° C. [25,28]. In this patent application we disclose the gas sensor properties of SnO disk-like structures. As demonstrated below, these disk-like structures exhibit nearly three orders of magnitude change in resistance upon exposure to nitrogen dioxide gas at temperatures below that typical for oxide chemiresistors. The observation of “Giant Chemo-Resistance” (GCR) in SnO, not dependent on nanosize dimensions, we believe, opens up a new class of promising materials with exceptional gas sensor capabilities and unique surface chemistry.

Disk-like structures were synthesized by a carbothermal reduction method using SnO₂ powder (Sigma-Aldrich, 99.9% purity) and carbon black (Union Carbide, >99% purity) in the molar ratio of 1.5:1(SnO₂:C). Optimized parameters used and details of this synthesis were previously reported [29]. Following synthesis, a dark wool-like material was removed from the inner walls of the alumina tube which had been maintained at a temperature between 350 and 450° C. Both SnO nanobelts and disk-like structures were obtained in this synthesis, but it was possible to separate them by a sedimentation process in isopropyl alcohol. The main focus of this work is on the sedimented material (i.e., the micro-disks) which was separated and dried at 50° C.

The morphological characteristics of the disk-like structures were examined by field emission scanning electron microscopy (FEG-SEM; JEOL, JSM-7500F). The phase and the crystallinity of the disk-like structures were studied by X-ray diffraction (XRD; Shimadzu, XRD 6000) using Cu Kα radiation and transmission electron microscopy (TEM; Philips, CM200) operated at 200 kV. Specific surface area was determined by the Brunauer-Emmett-Teller method (BET; Micromeritics instrument, ASAP 2000) under N₂ adsorption/desorption experiments [30]. For the gas sensing measurements, the SnO, collected from the sedimentation process, was dispersed in isopropyl alcohol with the aid of an ultrasonic cleaner. This was followed by dripping the suspension directly onto alumina substrates coated with interdigitated platinum electrode arrays (100 μm Pt fingers spaced 200 μm apart). The substrates were then heated to 100° C. for 15 min to evaporate the solvent. Gas sensing tests were carried out by monitoring changes in resistance (using an HP34970A data acquisition switch unit) during cyclic exposure to different concentrations of NO₂ (between 1 and 100 ppm) and H₂, CH₄ and CO (10 to 500 ppm) diluted in dry air (baseline gas). For this purpose, certified pre-mixed gas mixtures, containing a trace of the test gases diluted in dry air [NO₂ (100 ppm) and H₂, CH₄ and CO (1000 ppm)] (Air Gas) were mixed with clean dry air, using mass flow controllers (MKS). The total gas flow rate (test plus balance gas) was maintained constant (200 sccm) during all tests. The sensor test devices were equilibrated in dry air for 12 h at each temperature before the beginning of each gas sensor measurement to insure a stable and reproducible baseline resistance. Gas sensor measurements were performed in the range from 100 to 300° C. with steps of 50° C. and the sensor signal was defined as R_(gas)/R_(air) for oxidizing gases and as R_(air)/R_(gas) for reducing gases, where R_(air) is the material resistance in air atmosphere and R_(gas) is the material resistance under the analyte gas presence.

In order to study the disks' chemical stability during sensor test measurements, in situ X-ray Absorption Near Edge Spectroscopy (XANES) at the L-edge of Sn was performed during a simulated sensor test at the Brazilian Synchrotron Laboratory. To prepare the sample for XANES analysis, 2 mg of SnO disks were mixed with 50 mg of boron nitrite (BN) in an agate mortar. The powder was then pressed in a 12 mm diameter pellet at 8 MPa. The sample was mounted on a sample holder specially designed for in situ XANES measurements at high temperature, which was then introduced in a quartz tube furnace. XANES measurements were performed from 3900 to 4050 keV with sample maintained at 200° C. (best sensor response temperature). After reaching 200° C. under a N₂ gas flux of 100 sccm, the sample was stabilized for 3 h following which the first spectrum was taken. The N₂ was then substituted by dry air also at a flow rate of 100 sccm and another spectrum was taken after 30 min. Finally, the gas was switched back to pure N₂ and a final spectrum was taken after 1 h. The spectrum of a SnO₂ standard sample was also taken for comparison.

FIG. 1 presents FEG-SEM images of the collected material, following separation by sedimentation, showing it to be predominantly composed of disk-like structures with flat and smooth surfaces. These disks have diameters ranging from about 100 nm up to dozens of micrometers. The smaller disks (in general, disks less than 1 μm diameter—FIG. 1b ) exhibit an octagon-like faceted shape, while the larger disks are nearly perfectly circular in shape (FIG. 1c ). Most disks have diameters greater than 1 μm and these structures are similar to those reported previously in the literature [24,28].

FIG. 2a shows a low-magnification TEM image of a disk with diameter of about 200 nm and faceted shape. The inset in FIG. 2b presents the SAD pattern of this disk and the isolated spots obtained are typical of single crystalline materials. All of the spots in the SAD pattern can be indexed by the litharge structure of SnO (tetragonal) (JCPDS card #6-395), agreeing with XRD results (not shown here). FIG. 2b also shows an HRTEM image of the disk, confirming that each disk is single crystalline. Occasionally, misoriented particles can be found at the disks' extremities. The interplanar distance shown in FIG. 2b is 0.27±0.01 nm, related to the (110) planes of the tetragonal structure of SnO, as observed by SAD. Combining SAD and HRTEM results, it was possible to affirm that the larger facets are {110} planes while the smaller ones are {100} planes, which is the same orientation observed by Dai et al.[24]. Moreover, the larger faces of the disks must be the (001) planes, which is perpendicular to the zone axis of the diffraction pattern.

Typical gas response measurements (R_((NO2)/)R_((air))) taken at 200° C., as a function of time for periodic pulses of gases containing NO₂ ranging from 1 to 100 ppm, each pulse lasting 20 min, are shown in FIG. 3. The sensor based on SnO disk-like structures exhibited a remarkably strong response when exposure to NO₂ with an approximately 50-fold increase in resistance when exposed to 1 ppm NO₂ and nearly a 3 orders of magnitude response to 100 ppm NO₂. Given the exceptionally high sensitivities observed here, in combination with the fact that this is achieved without need for nano-structuring the material down to the 10 nm regime (see discussion below) and the chemosorption phenomenon nature related to it, we label this response “Giant Chemo-Resistance” (GCR).

For all levels of NO₂, the resistance (Rgas) initially increases abruptly when exposed to the analyte gas, followed by an asymptotic change to the steady state with a similar behavior, but slower, observed for the recovery process. This is a typical n-type semiconductor sensor response, although SnO has been reported previously to be a p-type material [26,27]. Clearly, a wide band gap semi-conductor such as SnO (Eg >2.5 eV) can be either n or p type, depending on the doping or redox level. Given that the SnO investigated in this study was synthesized by a carbothermal reduction method, it is not surprising that these SnO specimens may be more oxygen deficient than those reported earlier and thus exhibiting n-type behavior. Thermopower and Hall effect studies are planned to determine the carrier density. The sensor response to IOU ppm NO₂ versus temperature is shown plotted in FIG. 4, clearly demonstrating that the optimum operating temperature with respect to sensitivity is in the range of 200° C. This is presumably a consequence of the competition between slow gas adsorption kinetics at lower temperatures and enhanced desorption at higher temperatures [31].

To study the oxidation state and the chemical stability of disks under different atmospheres at 200° C., XANES measurements were performed under in situ conditions simulating the sensor test measurements. If any variation in the tin oxidation state should occur, a change in XANES spectrum would be observed. Curve a in FIG. 5 shows the XANES spectrum obtained for the sample after 3 h stabilization in pure N₂ flux. It has four main absorption peaks, labeled as i, ii, iii and iv, characteristic of the SnO material spectrum [32], thereby confirming the +2 oxidation state of Sn in the micro disks. Comparing this result to the SnO₂ standard shown by curve d in FIG. 5, it is clear that the SnO₂ signature (broad peak labeled 3,4,5) related to the 2p_(3/2)→6d transition, is not present in the XANES spectrum obtained for the SnO disks. Curve b in FIG. 5 shows the XANES spectrum for the SnO disk sample following a 30 min exposure to dry air atmosphere while curve c in FIG. 5 displays the spectrum obtained after 1 h stabilization in pure N₂ following the dry air exposure. No change in the spectrum occurs for the SnO sample using either inert or oxidizing atmospheres, indicating good chemical stability for the SnO disk-like structures. The stability against oxidation of SnO to SnO₂ at 200° C. was expected given that the observed degradation of SnO at about 400° C. is not an oxidation process, but a thermal activated decomposition process [25].

The sensor signal was found to follow a power law dependence on gas concentration of the form R∝p^(β) _(NO2) with β in this case taking on the value of 0.64. Assuming that this dependence continues to hold to lower NO₂ concentrations, a sensor response of ˜13 is estimated for an exposure to 100 ppb of NO₂ [9]. This easily satisfies the National Ambient Air Quality Standards (NAAQS) requirement of being able to detect 100 ppb per hour, the standard for public health protection set by the U.S. Environmental Protection Agency [33]. It is important to reiterate that this outstanding response was obtained at 200° C., well below the phase transition temperature observed for disk-like structures, therefore insuring stable operation [25]. Furthermore, given the micron rather than nanometer dimensions of these disks, their morphology should be less susceptible to coarsening with time and thereby less likely to exhibit short term aging affects. Moreover, the level of sensitivity to NO₂ obtained here is one of the highest reported for catalyst-free tin-based chemiresistors. Few other GCR response reports have been published using catalyst-free SnO₂ systems [11,34].

Gas measurements were also performed to investigate the selectivity of SnO disk-like structures to NO₂ versus other potential interferents. The sensor response for 100 ppm of NO₂, H₂, CO, and CH₄ in air at 200° C. is shown in the inset of FIG. 4. The sensor response was more than 200-fold larger for NO₂ than for H₂ and CO and nearly 1000-fold larger than to CH₄, demonstrating the remarkably high selectivity to NO₂ relative to these other common interference gases [21,35].

Gas sensor performance is highly influenced by surface area, with larger surface area leading to higher sensitivity [36,37]. In the present case, Brunauer-Emmett-Teller (BET) measurements shows a specific surface area of 8.0 m² g·⁻¹, which cannot explain the giant gas response observed for the SnO disk-like structures. Since the reports of Xu et al. in 1991 [38], showing markedly enhanced sensitivity of SnO₂ to CO and H₂ gases, as the dimensions of the SnO₂ particles decreased below 20-50 nm, many further reports of enhanced sensitivity of nanodimensioned metal oxide chemiresistive sensors have been reported [39,40]. These empirical observations were successfully modeled by Rothschild et al. [41] who took into account the unique characteristics of space charge regions in nanocrystalline semiconductors. This model accounts for the fact that when the radius of the grains, or the thickness of the film becomes smaller than the Debye length, typically on the order of 10 nm, the space charge regions generated at the crystallite or film surfaces overlap such that the entire volume of the crystallite or film becomes depleted of free charge carriers, leading to a much stronger modulation of resistance by adsorption of gases. While similar Debye lengths are calculated for SnO (λ_(D(SnO)˜)7-20 nm at 200° C., depending on carrier density), the much larger dimensions of the largely single crystalline SnO disk structures studied here, typically between 70 and 250 nm thick, suggest that charge carrier depletion across the whole thickness of the disks cannot be responsible for the GCR sensor response observed here.

Recently, it was demonstrated that the sensitivity of SnO₂-based sensors can be improved by exposing specific facets at the surface [12] i.e., specific crystallographic planes can lead to higher sensitivity due to their high chemical activity. As previously reported [24] and discussed further in this work, the SnO disks studied here are bi-dimensional structures with large (001) exposed surface planes. For litharge structures, it is known that the (001) plane exhibits a high fraction of electronic lone pairs [42,43].

According to recent DFT calculations, the sterically active lone pair, normally ascribed to the filled Sn 5s² orbital, shows instead that the states responsible for the asymmetric Sn electron distribution are due to the coupling of unfilled Sn(5p) with the antibonding combination arising from interaction of Sn(5d) and O(2p) orbitals. These lone pairs, with relatively high energy states at the top of the valence band, make the transfer of electrons to the adsorbed molecules more favorable [44]. The high density of such lone pair orbitals in the (001) surface plane may then explain the enhanced capacity of SnO to absorb oxidizing species such as NO₂, as well as its strong selectivity to oxidizing vs reducing gases.

The single crystalline SnO micro-disks disclosed herein, synthesized by a carbothermal reduction process, exhibited a nearly 1000-fold increase in resistance upon exposure to 100 ppm of NO₂ without addition of catalysts or dopants nor the existence of nano-sized dimensions. Moreover, the SnO displayed a greater than 100-fold selectivity to NO₂ over potential interferents including CO, H₂ and CH₄. The high sensor signal and exceptional selectivity for this novel sensor material are attributed to the existence of a high density of active lone pair electrons on the exposed (001) planes of the single crystalline SnO disks. This, thereby, identifies new means, not utilizing nano-dimensions, to achieve high gas sensitivity.

FIG. 6 is a schematic gas sensor in which a SnO disk is in a circuit to measure its electrical resistance. Resistance changes indicate the presence of a gas such as NO₂. The sensor may be operated either by maintaining a fixed voltage and measuring changes in current during gas exposure or maintaining a constant current and measuring the change in voltage.

It is recognized that modifications and variations of the present invention will be apparent to those of ordinary skill in the art and it is intended that all such modifications and variations be included within the scope of the appended claims.

The numbers in brackets refer to the references listed herein. The contents of all these references are incorporated herein by reference.

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What is claimed is:
 1. Gas sensor comprising: a single crystalline SnO disk; and circuitry for measuring electrical resistance of the disk, whereby change in resistance indicates adsorption of a gas on the disk's surface, wherein the SnO disk has a [001] plane that includes a plurality of a lone pair orbitals that enhances the capacity of the SnO disk to absorb oxidizing species exhibiting both thermal and chemical stability for temperatures below 400° C., the circuitry maintains a fixed voltage and measures the change in current during exposure of the gas onto the SnO disk, or maintains a fixed current and measures the change in voltage during exposure of the gas unto the SnO disk to assess the electrical resistance of the SnO disk.
 2. The gas sensor of claim 1 wherein the disk has a diameter in the range of approximately 100 nanometers to 100 μm.
 3. The gas sensor of claim 1 wherein the gas is NO₂. 